Condensation product of castor oil with half ester of maleic acid



Patented May 25, 1937 CONDENSATION PRODUCT OF CASTOR OIL WITH HALF ESTER OF MALEIO ACID Herman A. Bruson, Germantown, Pa", assignor to The Resinous Products & Chemical 00. Inc.,

Philadelphia, Pa.

-No Drawing. Application May'10, 1932,

' Serial N0. 610,504 I 28 Claims.

This invention describes a method of preparing lose. with or without other resins to form lacquers Y which give clear, homogeneous, elastic films that l5. adhere well to'metal or wood surfaces.

' Still a further object is to produce a non-spewing derivative of castor oil for use as a nitrocelluloseplasticizer in coatings for fabrics, artificial leather, natural leather, paper, linoleum, rubber- 20 ized fabric, regenerated cellulose, and the li e.

Another object is to provide a plastic r bberlike derivative of castor oil which, in the presence of siccatives possesses drying properties somewhat like linseed oil, and which may be mixed 5 directly with oleo-resinous varnishes as an adjunct to or in lieu of the commonly used drying oils, in order to obtain non-yellowing coating compositions of extreme flexibility.

It has been known for some time that maleic '30 acid as well as other polycarboxylic acids may be condensed with polyhydric alcohols such as glycerol or glycols to form so-called alkyd resins and that such condensations can be carried out in the presence'of castor oil with or without the use 35 of other fatty oils, alcohols, fatty acids, resins, etc., to yield resinous bodies which may be used in nitrocellulose lacquers. (U. 'S. Patents 420; 1,783,167; 1,807,503.) Such prior processes 40 involve the use in every case of polyhydric alcohols so as to produce with the, polybasic acid, a fundamental resin complex which is modified. by and dispersed in the'castor oil. Depending upon the kind of polybasic acid used as' well as upon 45 the nature "of the polyhydric alcohol, a given quantity of' castor oil will yield entirely different resins. In general the aromatic polycarboxylic acids with polyhydric alcohols and castor oil yield either hard,jtough resins or sticky sirups which- Q upon ageing in the form of films or coatings become progressively more and more brittle. The aliphatic polycarboxylic acids having long chains over 6 carbons such as sebacic acid, yield soft, tough, rubber-like masses or oily sirups which do 55 not become brittle upon ageing. However, all of quers or varnishes.

these products possess certain limitations. They are for example incompatible with certain hard, natural and synthetic resins such as modified i ester -gums and phenol-'formaldehyde-rosin esters which are used in large quantities in nitrocellu- 5 lose lacquersv They furthermorev are generally incompatible when mixed in cold with oleo-resinous paints or varnishes and require for their solutions aromatic hydrocarbons such as toluene or xylene rather than the conm'lonly used cheap var- 10 nish thinners of aliphatic nature such as petroleum naphtha. These limitations are completely absent in the products made according to the present invention as described in more detail below.

It has furthermore been proposed to heat castor oil with maleic acid (or maleic anhydride) alone, to obtain completely insoluble rubbery masses, (German Patent 479,965 (1929)) which can be made soluble in oils or resins onlyby heating with the latter during the condensation and which likewise then yield completely insoluble linoxyn-like materials. On account of their insolubility such materials cannot be used in lac- According to the present invention however,

products are obtained whichare totally different from any of the above types; They are first of all not made from any polyhydric alcohols whatsoever. They are furthermore exceedingly soluble in most organic solvents including petroleum naphtha, and are compatible with practically all of the hard, natural or synthetic resins atriresent available which are themselves compatible with nitrocellulose solutions. In addition these new 5 products are readily soluble in and compatible with odrinary or bodied drying oils, and with paints and oleo-resinous varnishes prepared from drying oils. They embrittle only very slightly on ageing in the form of films or coatings and can be baked to give hard, tough elastic films. They thus have a wide sphere of usefulness in preparing coatings of the most diverse nature. I

In.practicing this invention, castor oil (raw, air-blown, or heat-bodied) is heated with a half ester of maleic acid such as is obtained by 'condensing' one mole of a monohydric alcohol with maleic anhydride or maleic acid. Such half esters are usually crystalline substances, soluble in sodium carbonate solution. The condensation is effected at a temperature preferably between 150 Csand 250 C. usually 200 C. in a vessel eguipped with an agitator and an outlet for the watervapor formed. The proportion of castor oil-to maleic half ester may vary within wide 55 Such compositions resins such as ester gum,

In most cases it is not necessary to isolate the half ester of maleic acid for use in this condensation, as the same result maybe obtained by-heating castor oil with maleic acid or maleic anhydride and a monohydric alcohol, the maleic half ester being formed in situ during the hea'tingand ultimately condensing further with the castor oil.

The monohydric alcohols preferably usedare those boiling above 150 C. such as cyclohexanol,

octyl alcohoL-hexyl alcohol, clapryl alcohol, benzyl alcohol, borneol, fenchol, alpha-terpineol, glycol monobutyl ether C4HaO-CH2CH2OH, diethyltoluene was formed.

ene glycol-monobutyl ether C4HoO-CHzCH2-OCH2CHzOH. diethylene glycol-monoethyl ether C2H6-OCH2CH2OCH2-CH2OH,

.oelic alcohol, cetyl alcohol, octadecanol, and the mixed higher alcohols of boiling range 190- 250 C. which are obtained as a by-product in the manufacture of synthetic methanol from hydrogen and carbon monoxide and consisting essentially of aliphatic methy and dimethylderivatives-of primary and secondary alcohols higher than heptyl alcohol.

The products obtained vary in their fllm characteristics somewhat from each other, depending upon the particular alcohol used and the ratio of the castor oil to the maleic half ester. They are all extremely viscous rubbery sirups which dissolve in benzene, toluene, acetone, vbutyl acetate, petroleum naphtha and linseed oil. They are heat reactive and if heated for a considerable period of time (3-4 hours at 100 C.) lose their solubility in organic solvents and form tough, soi't, plastic-masses having adhesive properties. Those made from half esters of maleic acid with terpenic alcohols show unusual drying properties in the presence 01' siccatives I dry in 24 hours to pale flexible films which discolor only slightly on ageing. This behavior was entirely unexpected as castor-oil or heat-bodied castor oils are non-drying oils under the same conditions.

In their soluble form these plastic materials may be heated with waxes to produce petrolatumlike substances having useful propertiesinprinting inks and in coatings for finishing textiles. Their properties may be modified by heating with 'iatty oils such as sardine oil, olive oil, cotton seed oil.

rape seed oil, linseed oil, tung oil, soya bean oil.

and the like, for special purposes. All-oi. these combinations when incorporated in nitrocellulose lacquers give non-spewing fllms characterized by extreme softness and flexibility and free from the rancid odor of castor oil. They may likewise be heated or mixed with other natural or synthetic rosin, dammar, fossil gums, or alkyd resin to flexibilizethe same.

In the following examples, typical methods for making these resins are given:

ExampteI 310 grams raw-castor oil-is mixed with 152 grams or mono-octylmale'ate (obtained by condensing maleic anhydride with-one mole equivalent or then without reflux for such as cobalt resinate.

octyl alcohol) and the mixture heated in an open vessel with stirring at 190-200 C. At first a thin liquid forms but as heating continues, it

viscous and sticky a very heavy, pale becomes increasingly more until after about 3 hours rubbery liquid is obtained. solved in toluene or butyl acetate to give an solution of the material. It is readily compatible with solutions of nitrocellulose and in the proportions of 1 part nitrocellulose (dry) to 2 parts of the material gives elastic tough fllmshaving good physical properties. I

' Example 2 373 grams castor oil (air-blown) is mixed with 83 grams maleic anhydride and 140 grams of the monobutylether of diethylene glycol. Heated to 110 C. under reflux condenser for about 6 hours then gradually to 210 C. without reflux for about 2 hours until a soft rubbery mass soluble in V reflux condenser with a mixture of 93 grams grams commercial alphamaleic acid and ,62 terpineol at 180-l90 C. for about 1 hour and about 2 hours until a viscons material having a viscosity .l" (Gardner- Holt scale) when out 50% with toluene was obtained. The product was mixed with 1% or its weight 01' cobaltresinate drier dissolved in a little petroleum naphtha. It behaves like a drying oil when exposed to the air. The product may be blended directly with drying oils or oleo-resinous varnishes to produce toughened fllms which when baked at 300 to 400 F. form insoluble coatings. For example a varnish-made from pounds oi a natural or synthetic resin and 20 gallons oi drying oil may be mixed with 100 pounds of the above plastic material to produce a varnish which when mixed with cobalt resinate slccative dries tack free within 24 hours.

' Example 4 373 grams heat bodied castor oil is heated with a mixture of 46 grams maleic acid, '47 grams cetyl alcohol and 25 grams Japan wax to 190- 195? C. for 9 hours until a sort rubbery mass soluble in benzene is formed.

Example 5 Example 6 310 grams raw castor oil, 100 grams maleic anhydride and 100 grams cyclohexanol are heated together for about 1 hour at C. then gradually during 2 hours to C. in an open vessel.

The. temperature is then raised to 205 C. and

held thereat for about 3 hours until a viscous rubbery substance soluble in toluene is obtained.

Example 7 373 grams raw castor oil; 93 grams maleic acid and 146.4,grams of higher alcohols (13. P. 250? C.) from the methanol together at 190-200 C. in an open vessel for several hours-until a benzene-soluble rubber-like masswas obtained.

oil (or any drying synthesis were heated This may be dis- In the above examples numerous modifications in the proportions and the nature of the ingredients may be made without departing from the scope of the invention which is limited only in the claims that follow. To anyone'versedin the art it is evident that other temperatures can be employed and that wide variations are possible. Reduced pressures can be used with good results.

Mixtures of more than one maleic half ester may be used in the condensations. The use of an excess of monohydric alcohol over thattheoretically necessary to combine with one maleic. acid carboxyl group is also included herein as in this case neutral, non-harmful diesters of maleic acid are produced in admixtures with the plastic condensation product. The. condensations may be carried out in the presence of inert high boiling solvents such as petroleum naphtha or amylbenzene; and rosin, ester gum, or other natural or artificial resins may. be added to produce varnishlike materials. In addition to the oils, waxes, and resins, other compounds such as soaps, driers and pigments may be incorporated with the products obtainable as described herein.

What I claim is: 1

1. A composition of matter consisting of a condensation product of castor oil, an alcohol containing only one hydroxyl group, and a member of the group consisting of maleic acid and maleic anhydride.

2. A composition of matter consisting of a condensation product of castor oil with a maleic acid half ester of an alcohol containing only one hydroxyl group.

3. A composition of matter consisting of a condensation product of castor oil, maleic acid, an alcohol containing only one hydroxyl group and one of the group consisting of fatty oils and waxes.

4. A composition of matter consisting of a condensation product of castor oil, alpha-terpineol, and maleic acid.

5. A composition of matter consisting of a condensation product of castor oil, monobutylether of diethylene glycol, and maleic acid.

6. A composition of matter. consisting of a condensation product of castor oil, an alcohol containing only one hydroxyl group boiling above 150 C. and a member of the group consisting of maleic acid and maleic anhydride.

7. A composition of matter consisting of a condensation product of castor oil, maleic acid, and

an .octyl alcohol.

8. A process which comprises heating at reaction temperature, a mixture of castor oil, an alcohol containing only one-hydroxyl group, and a member of the group consisting of maleic acid and maleic anhydride. r

9. A process which comprises heating at reaction temperature, -a mixture of castor oil and a maleic acid half ester of an alcohol containing only one hydroxyl group.

10. A process which comprises heating at reaction temperature, a mixture of castor oil, maleic acid, an alcohol containing only one hydroxyl group, and a wax. 7

11. A process which comprises heating at reaction temperature, a mixture of castor oil, maleic acid, an alcohol containing only one hydroxyl group, and a fatty oil. a

12. A process-which comprises heating at about 150-230 C.' a mixture of castor oil, an alcohol containing only one hydroxyl group boiling above 150 C. and a member of the group consisting of maleic acid and maleic anhydride. I

13. A process which comprises heating at about 150-250" 0. a mixture of castor 011 and a half ester of maleic acid and an alcohol containing only one hydroxyl group, said alcohol boiling above 150 C.

14. The process which comprises heating at reaction temperature a mixture of castor oil, alphaterpineol, and maleic acid.

15. The process which comprises heating at recomprises heating at reaction temperature, a

mixture of castor oil, a maleic acid half ester of an alcohol containing only one hydroxyl group,-

and a fatty oil.

19. A process which consists in 1) heating an alcohol containing only one hydroxyl group with maleic anhydride so as to form a maleic acid half ester arid (2) subsequently, condensing said half ester with castor oil, so as to obtain a product soluble in hydrocarbons.

20. A process which consists in (1) heating maleic anhydride with a glycol ether containing only one 'free hydroxyl group so as to form a maleic acid half ester and (2) subsequently, condensing said half ester with castor oil and a member of the group consisting of fatty oil glycerides and waxes.

21. A composition of matter consisting of a condensation product of castor oil and a mono ester obtainedfrom maleic acid and a saturated monohydric alcohol.

22. A condensation product of castor oil, a member of the group consisting of maleic acid and its anhydride and a monohydric alcohol of the general formulaR--OH--in which R represents a member of the group consisting of aliphatic and alicyclic hydrocarbon radicals and glycol ether groups. v

23. A condensation product and castor oil, a member of the group consisting of maleic acid and maleic anhydride, and an aliphatic alcohol containing only one hydroxyl group.

24. A condensation product of castor oil, a member of the group consisting of maleic acid and maleic anhydride, and a monohydric terpene alcohol.

25. A condensation product of castor oil and a mono ester obtained from maleic acid and an aliphatic alcohol containing only one hydroxyl p- I 26. A condensation product of castor oil and the reaction product of maleic anhydride and a monohydric terpene alcohol.

27. A condensation product obtained by the joint condensation of castor oil, maleic acid or its anhydride, and an aliphatic or alicyclio alcohol containing only one hydroxyl group.

28. A condensation product obtained by the joint condensation of castor oil, maleic acid or its anhydride, and a monohydric terpene alcohol.

HERMAN A. BRUsoN.

. CERTIFICATE OF CORRECTION.

Patent No. 2,081,266. May 25,- 1957.

- HERMAN A. BRU SO N.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 27, for "oelic" read oleic; page 5, second column,

line 51, claim 23, for "and" read of; and, that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent 0ffice. v

Signed and sealed this 31st (1a; of August A. D. 1937.

Leslie Frazer (Seal) Acting Commissioner of Patents. 

